CN111630373A - Light measurement device and light measurement method - Google Patents
Light measurement device and light measurement method Download PDFInfo
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- CN111630373A CN111630373A CN201880087284.9A CN201880087284A CN111630373A CN 111630373 A CN111630373 A CN 111630373A CN 201880087284 A CN201880087284 A CN 201880087284A CN 111630373 A CN111630373 A CN 111630373A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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Abstract
A spectrometry device (1) is provided with: a light source (2) that outputs excitation light; an integrator (3) having an internal space (11) in which a long-afterglow light-emitting material (S) is disposed, and outputting detection light from the internal space (11); a spectroscopic detector (4) that acquires spectral data of the detected light; an analysis unit (21) which analyzes the luminescence quantum yield of the long afterglow luminescent material (S) based on the spectral data; and a control unit (22) that controls the switching of the presence or absence of the input of excitation light to the internal space (11) and the exposure time in the spectroscopic detector (4); a control unit (22) for controlling the timing of the 1 st period (T)1) Maintains the input of the exciting light into the inner space (11) and in the 2 nd period (T)2) The light source (2) is controlled to stop the input of the exciting light into the internal space (11) and the exciting light is controlledPeriod 2 (T)2) Inner exposure time (t)2) Longer than the 1 st period (T)1) Inner exposure time (t)1) The spectral detector (4) is controlled in such a way.
Description
Technical Field
The present invention relates to a light measurement device and a light measurement method.
Background
As a measurement object of a spectroscopic measurement apparatus, long-afterglow luminescent materials such as a light-storing material and a phosphorescent material have attracted attention. The long-afterglow light-emitting material is a material that accumulates excitation light of sunlight, a fluorescent lamp, or the like, and emits light for a certain period of time even after the irradiation of the excitation light is stopped. In recent years, non-patent document 1 reports the first organic light-storing material in the world containing no rare earth element. The organic light storage material realizes the light emitting life of more than 1 hour under the room temperature condition by mixing 2 organic materials. Under such circumstances, it is considered that the application of the long-afterglow luminescent material to various fields such as safety displays, guide marks, timepiece dials, life saving tools, interior decorations, and cell imaging will be increasingly studied in the future.
Documents of the prior art
Non-patent document
Non-patent document 1: nature,2017, doi:10.1038/Nature24010, R.Kabe and C.Adachi
Disclosure of Invention
Problems to be solved by the invention
One of evaluation items of the luminescent material is a luminescence quantum yield. The luminescence quantum yield is a value representing the luminescence efficiency of the luminescent material. The emission quantum yield is calculated by dividing the number of photons emitted from the light-emitting material by the number of photons absorbed by the light-emitting material. However, the long-afterglow light-emitting material has a problem that the intensity of emitted light is significantly low compared to the intensity of excitation light, and the intensity of emitted light changes with time after the irradiation of excitation light is stopped. Therefore, it is difficult to accurately measure the luminescence quantum yield by the conventional method.
The present invention has been made to solve the above-described problems, and an object thereof is to provide a spectroscopic measurement apparatus and a spectroscopic measurement method capable of accurately measuring the luminescence quantum yield of a long afterglow luminescent material.
Means for solving the problems
A spectrometry device according to an aspect of the present invention is a spectrometry device for measuring an emission quantum yield by irradiating a long afterglow light emitting material with excitation light, including: a light source that outputs excitation light; an integrator having an internal space in which the long-afterglow luminescent material is disposed, the integrator outputting light from the internal space as detection light; a spectroscopic detector that disperses the detection light to obtain spectral data; an analysis unit that analyzes the luminescence quantum yield of the long afterglow luminescent material based on the spectral data; and a control unit that controls switching of the presence or absence of input of the excitation light to the internal space and the exposure time of the detection light in the spectroscopic detector; the control unit controls the light source so as to maintain the input of the excitation light into the internal space during a 1 st period in which the spectroscopic detector starts acquiring the spectral data and to stop the input of the excitation light into the internal space during a 2 nd period subsequent to the 1 st period, and controls the spectroscopic detector so that the exposure time of the detection light during the 2 nd period is longer than the exposure time of the detection light during the 1 st period.
In this spectrometry device, excitation light is continuously input to the long afterglow luminescent material in the integrator during the 1 st period when the acquisition of spectral data is started. The intensity of the excitation light is significantly higher compared to the intensity of the luminescence of the long afterglow luminescent material. Therefore, the exposure time of the detection light in the 1 st period is shorter than the exposure time of the detection light in the 2 nd period, whereby saturation of the signal in the spectral detector can be prevented. In the spectroscopic measurement apparatus, in the 2 nd period subsequent to the 1 st period, the input of excitation light to the long afterglow luminescent material in the integrator is stopped, and the exposure time of the detection light in the 2 nd period is made longer than the exposure time of the detection light in the 1 st period. Thus, light emission from the long-afterglow light-emitting material, which has a low intensity as compared with excitation light and whose intensity fluctuates with time after the input of excitation light is stopped, can be detected at a sufficient S/N ratio. Therefore, the spectroscopic measurement apparatus can measure the luminescence quantum yield of the long afterglow luminescent material with high accuracy. Further, by making the exposure time of the detection light in the 2 nd period longer than the exposure time of the detection light in the 1 st period, it is possible to suppress an increase in the amount of data necessary for acquiring spectral data even when the emission lifetime of the long-afterglow light-emitting material is long.
The control unit may control the spectral detector so that the exposure time for detecting light becomes longer after a predetermined time has elapsed from the start of the 2 nd period. In this case, an increase in the amount of data required to acquire the spectral data can be more preferably suppressed.
The spectroscopic detector may acquire the intensity peak of the excitation light and the intensity peak of the light emission of the afterglow light-emitting material in the 1 st period based on the spectral data, and the control unit may determine the exposure time of the detection light at the start of the 2 nd period based on the product of the ratio of the intensity peak of the excitation light to the intensity peak of the light emission and the exposure time of the detection light in the 1 st period. By using such a ratio, the exposure time of the detection light at the start of the 2 nd period can be optimized, and saturation of the signal in the partial emission detector in the 2 nd period can be prevented.
The analysis unit may analyze a time profile (profile) of the emission intensity of the long-afterglow luminescent material by normalizing the intensity of the emission of the long-afterglow luminescent material in the 1 st period based on the exposure time of the detection light in the 1 st period and normalizing the intensity of the emission of the long-afterglow luminescent material in the 2 nd period based on the exposure time of the detection light in the 2 nd period. Thus, even when the exposure time is dynamically changed during the measurement period, the time curve of the emission intensity of the long-afterglow light-emitting material can be accurately analyzed.
Alternatively, the integrator may be an integrating hemisphere. Even in the case of using an integrating hemisphere as an integrator, the luminescence quantum yield of the long afterglow luminescent material can be measured with good accuracy.
A spectroscopic measurement method according to an aspect of the present invention is a spectroscopic measurement method for measuring an emission quantum yield by irradiating a long afterglow light emitting material with excitation light, the spectroscopic measurement method including: a spectral data acquisition step of obtaining spectral data by splitting detection light output from an integrator having an internal space in which a long-afterglow light-emitting material is disposed, by a spectral detector; and a luminescence quantum yield analysis step of analyzing the luminescence quantum yield of the long afterglow luminescent material based on the spectral data; in the spectral data acquisition step, the input of excitation light into the internal space is maintained during a 1 st period in which the acquisition of spectral data by the spectroscopic detector is started, and the input of excitation light into the internal space is stopped during a 2 nd period following the 1 st period, so that the exposure time of the detection light in the 2 nd period in the spectroscopic detector is longer than the exposure time of the detection light in the 1 st period.
In this spectroscopic measurement method, excitation light is continuously input to the long-afterglow luminescent material in the integrator during the 1 st period when acquisition of spectral data is started. The intensity of the excitation light is significantly higher compared to the intensity of the luminescence of the long afterglow luminescent material. Therefore, the exposure time of the detection light in the 1 st period is shorter than the exposure time of the detection light in the 2 nd period, whereby saturation of the signal in the spectral detector can be prevented. In the spectroscopic measurement method, in the 2 nd period subsequent to the 1 st period, the input of excitation light to the long-afterglow light-emitting material in the integrator is stopped, and the exposure time of the detection light in the 2 nd period is made longer than the exposure time of the detection light in the 1 st period. Thus, light emission from the long-afterglow light-emitting material, which has a significantly low intensity with respect to the excitation light and whose intensity fluctuates with time after the input of the excitation light is stopped, can be detected at a sufficient S/N ratio. Therefore, in the spectroscopic measurement method, the luminescence quantum yield of the long afterglow luminescent material can be measured with high accuracy. By making the exposure time of the detection light in the 2 nd period longer than the exposure time of the detection light in the 1 st period, it is possible to suppress an increase in the amount of data necessary for acquiring spectral data even when the emission lifetime of the long-afterglow light-emitting material is long.
In the spectral data acquisition step, the exposure time of the detection light in the spectroscopic detector may be made longer after a predetermined time has elapsed from the start of the period 2. In this case, an increase in the amount of data required to acquire the spectral data can be more preferably suppressed.
The spectroscopic measurement method may further include a peak acquisition step of acquiring an intensity peak of the excitation light and an intensity peak of the light emission of the long-afterglow light-emitting material in the 1 st period based on the spectral data, and in the spectral data acquisition step, the exposure time of the detection light at the start of the 2 nd period may be determined based on a product of a ratio of the intensity peak of the excitation light to the intensity peak of the light emission and the exposure time of the detection light in the 1 st period. By using such a ratio, the exposure time of the detection light at the start of the 2 nd period can be optimized, and saturation of the signal in the partial emission detector in the 2 nd period can be prevented.
In the luminescence quantum yield analysis step, the time curve of the luminescence intensity of the long-afterglow luminescent material may be analyzed by normalizing the intensity of the luminescence of the long-afterglow luminescent material in the 1 st period based on the exposure time of the detection light in the 1 st period and normalizing the intensity of the luminescence of the long-afterglow luminescent material in the 2 nd period based on the exposure time of the detection light in the 2 nd period. Thus, even when the exposure time is dynamically changed during the measurement period, the time curve of the emission intensity of the long-afterglow light-emitting material can be accurately analyzed.
In addition, an integrating hemisphere may also be used as an integrator. Even in the case of using an integrating hemisphere as an integrator, the luminescence quantum yield of the long afterglow luminescent material can be measured with good accuracy.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, the luminescence quantum yield of the long afterglow luminescent material can be measured with high accuracy.
Drawings
Fig. 1 is a schematic diagram showing an embodiment of a spectroscopic measurement apparatus.
FIG. 2 is a graph showing the principle of calculation of luminescence quantum yield.
FIG. 3 is a graph showing the temporal change in the intensity of luminescence in a long-afterglow luminescent material.
Fig. 4 is a diagram showing an example of control of the time profile of the intensity of light emission and the exposure time of detection light in the long afterglow light emitting material.
Fig. 5 is a diagram showing an example of calculation of the number of absorbed photons of the long afterglow luminescent material.
Fig. 6 is a diagram showing an example of calculation of the number of luminescent photons of the long-afterglow luminescent material.
Fig. 7 is a schematic diagram showing another embodiment of the spectrometry apparatus.
Detailed Description
Hereinafter, preferred embodiments of a spectrometry device and a spectrometry method according to an aspect of the present invention will be described in detail with reference to the drawings.
Fig. 1 is a schematic diagram showing an embodiment of a spectroscopic measurement apparatus. As shown in the figure, the spectrometry device 1 includes a light source 2, an integrator 3, a spectroscopic detector 4, and a computer 5. The spectrometry device 1 is a device for measuring the luminescence quantum yield of the luminescent material. The luminescent material as the object to be measured is a long afterglow luminescent material such as a light storage material or a phosphorescent material. The long-afterglow light-emitting material is a material that accumulates excitation light of sunlight, a fluorescent lamp, or the like, and emits light for a certain period of time even after the irradiation of the excitation light is stopped. Examples of the long persistence light-emitting material include inorganic materials and organic materials containing rare metals. The form of the long-afterglow luminescent material can adopt various forms such as solution, film, powder and the like.
The light source 2 is a device that outputs excitation light. The excitation light output from the light source 2 is light having a wavelength at which the long afterglow luminescent material is excited to emit light. The light source 2 is, for example, a monochromatic light source having a monochromator attached to a xenon lamp. The light source 2 may be constituted by a laser diode that outputs laser light having a wavelength corresponding to the absorption wavelength of the long afterglow light emitting material. The light source 2 may also be a wavelength variable light source. The light source 2 may also include an ND filter, a relay optical system, a shutter, and the like. The light source 2 may be configured to be capable of outputting standard light for sensitivity correction of the entire apparatus.
The integrator 3 includes: a main body 12 having an internal space 11 in which the long afterglow luminescent material S is disposed; an input section 13 that inputs the excitation light output from the light source 2 to the internal space 11; and an output unit 14 for outputting the light from the internal space 11 to the outside. In the present embodiment, the integrator 3 is an integrating sphere, and the main body 12 and the internal space 11 are formed in a spherical shape. The spherical portion of the inner wall of the body 12 is a wall surface having high reflectance and excellent diffusibility, and the flat surface portion is a flat mirror having high reflectance.
The main body 12 is provided with a sample mounting portion 15. A holding container for holding the long afterglow luminescent material S is attached to the sample mounting portion 15. For example, when the long afterglow luminescent material S is a liquid, a cell (cell) for a solution sample made of a transparent material (e.g., quartz glass, plastic, or the like) that transmits light is attached to the sample attachment portion 15 as a sample container. In the case where the long-afterglow luminescent material S is a solid such as a powder or a thin film, a solid sample cell made of a transparent material (e.g., quartz glass, plastic, etc.) or metal that transmits light is attached to the sample attachment portion 15 as a sample container.
The long-afterglow luminescent material S may not necessarily be disposed entirely in the internal space 11 of the integrator 3, and a part of the long-afterglow luminescent material S may be disposed in the internal space 11 of the integrator 3. For example, a sample disposed outside the inner wall of the integrator 3 may be optically disposed in the internal space 11 of the integrator 3 using an optical attachment attached to the sample mounting portion 15.
The input unit 13 inputs excitation light to the internal space 11. The input unit 13 is optically connected to the light source 2 by an input light guide 16. As the input light guide 16, for example, an optical fiber or the like can be used. In addition, the output section 14 outputs light from the internal space 11. The output unit 14 is optically connected to the photodetector 4 by an output light guide 17. As the output light guide 17, for example, an optical fiber or the like can be used.
In the integrator 3, the excitation light from the light source 2 is input from the input unit 13 to the internal space 11, and the excitation light is multiply diffused and reflected in the internal space 11. In the integrator 3, light emission generated by irradiation of the long afterglow light emitting material S with excitation light is multiply diffused and reflected in the internal space 11. The excitation light and the emission light that have undergone multiple diffuse reflections in the internal space 11 are input as detection light from the output unit 14 to the spectroscopic detector 4.
The spectral detector 4 spectrally separates the detection light output from the integrator 3 to acquire spectral data. The spectroscopic detector 4 separates the detection light into wavelength components by a spectroscopic element such as a grating or a prism, and detects the intensities of the separated wavelengths of light by a group of optical sensors. The photosensor group is configured by one-dimensionally arranging a plurality of light receiving sections, for example. The photosensor group detects the intensity of light of the wavelength component by the light receiving part corresponding to each wavelength, and acquires spectral data of the excitation light and the emission light, respectively. The spectroscopic detector 4 outputs the acquired spectral data to the computer 5.
As the optical sensor of the spectroscopic detector 4, a CCD linear image sensor or a CMOS linear image sensor formed on a silicon substrate is used. These sensors have a sensitivity to light with a wavelength of, for example, 360nm to 1100 nm. Further, as the optical sensor of the spectroscopic detector 4, an InGaAs linear image sensor is exemplified. The sensor has sensitivity to light having a wavelength of 900nm to 1650nm, for example. The spectral detector 4 can variably set the exposure time for detecting light, and the exposure time in measurement can be changed based on a predetermined condition (described below).
The computer 5 includes a memory such as a RAM or a ROM, a processor (arithmetic circuit) such as a CPU, a communication interface, and a storage unit such as a hard disk. Examples of the computer 5 include a personal computer, a microcomputer, a cloud server, a smart device (a smart phone, a tablet terminal, or the like), and the like. The computer 5 includes a display unit 18 such as a monitor and an input unit 19 such as a keyboard and a mouse.
The computer 5 functions as the analysis unit 21 and the control unit 22 by executing a program stored in a memory by a CPU of a computer system. The analysis section 21 performs analysis of the luminescence quantum yield of the long afterglow luminescent material S based on the spectral data of the excitation light and the luminescence light obtained by the spectroscopic detector 4. The control unit 22 controls the light source 2 and the spectral detector 4. The control unit 22 controls the operation of the light source 2 and switches the presence or absence of input of excitation light to the internal space 11. The control unit 22 controls the spectroscopic detector 4 to control the exposure time of the detection light in the spectroscopic detector 4. Details of the control are described below.
Next, a method for measuring the luminescence quantum yield of the long afterglow luminescent material S using the above spectroscopic measuring apparatus 1 will be described.
In this measurement method, the above-described reference measurement and sample measurement are performed separately. The sample measurement is configured to include a spectrum data acquisition step (step S01) and a luminescence quantum yield analysis step (step S02). The spectral data acquisition step is a step of obtaining spectral data by splitting the detection light output from the integrator 3 having the internal space 11 in which the long-afterglow luminescent material S is disposed, by the spectroscopic detector 4. The luminescence quantum yield analysis step is a step of analyzing the luminescence quantum yield of the long afterglow luminescent material S based on the spectral data.
The luminescence quantum yield is one of evaluation items of a luminescent material, and is a value indicating the luminescence efficiency of the luminescent material. In general, if excitation light is absorbed by a light-emitting material, light emission such as fluorescence or phosphorescence and heat emission by radiationless transition are performed. Luminescence quantum yield phiPLThe number of photons N emitted from the light-emitting material is expressed by the degree of light emissionLDivided by the number of photons absorbed by the luminescent material NAAnd then calculated.
FIG. 2 is a graph showing the principle of calculation of luminescence quantum yield. In the figure, the horizontal axis represents wavelength and the vertical axis represents intensity, and the spectrum S1 at the time of reference measurement and the spectrum S2 at the time of sample measurement are plotted, respectively. The reference measurement is a step of acquiring spectral data of the detection light without disposing the long-afterglow luminescent material S in the internal space 11 of the integrator 3. In the reference measurement, excitation light is continuously input to the integrator 3 in the measurement. The spectrum S1 acquired in the reference measurement corresponds to the spectral data of the excitation light output from the light source 2.
The sample measurement is a step of acquiring spectral data of the detection light by disposing the long-afterglow luminescent material S in the internal space 11 of the integrator 3. In the sample measurement, excitation light is input to the integrator 3 for a predetermined time from the start of measurement, and the output of excitation light is stopped after the elapse of the predetermined time. Thereafter, the measurement is terminated when the luminescence of the long-afterglow luminescent material S exceeds a threshold value and then decays.
Among S1 obtained in the reference measurement, a spectrum S1 appearing on the short wavelength side (here, about 300nm to 400nm)aCorresponding to the component of the excitation light. Among S1 obtained in the reference measurement, S1 appears in a spectrum different from the spectrumaSpectrum S1 of the wavelength region (here, about 480nm to 650nm)bCorresponding to the component of the excitation light (or background light) in the detection light. Among the spectra S2 obtained in the sample measurement, the spectrum S1 appearedaSpectrum S2 of the corresponding wavelength regionaCorresponding to spectral data of the component of the excitation light in the detection light. Among the spectra S2 obtained in the sample measurement, the spectrum S1 appearedbSpectrum S2 of the corresponding wavelength regionbCorresponding to spectral data of a component detecting light emission in the light. Thus, the number of photons N absorbed by the luminescent materialABased on self-spectrum S1aMinus spectrum S2aThe number of photons N emitted from the light-emitting material was calculated from the obtained region R1LBased on self-spectrum S2bMinus spectrum S1bThe obtained region R2.
When the long-afterglow light-emitting material S is used as a measurement target, the intensity of light emitted from the long-afterglow light-emitting material S is significantly (approximately one digit) lower than the intensity of excitation light, and the intensity of light emitted after stopping irradiation of excitation light changes with time. For example, fig. 3 is a graph obtained by plotting a spectrum S1 obtained in the reference measurement and a plurality of spectra S2 obtained by performing a plurality of sample measurements at regular time intervals. In the case of a general luminescent material, even when a plurality of sample measurements are performed, the spectrum corresponds to the spectrum S2bHardly changes, but in the result of FIG. 3 for the long-afterglow luminescent material S, the spectrum S2bThe number of photons represented increases each time a sample measurement is performed. Therefore, it is understood that the luminescence quantum yield of the long afterglow luminescent material S in this case gradually increases with time.
When the luminescence quantum yield of the long afterglow luminescent material S is measured, the exposure time of the detection light in the spectroscopic detector is constant throughout the period from the start of measurement to the end of measurement in the conventional measurement method. This exposure time is set in a short time of, for example, several tens of msec, in order to avoid saturation of a signal in the spectroscopic detector by excitation light, but if detection of detection light is performed in the same exposure time after the excitation light output is stopped, the S/N ratio for detection of light emission of the long afterglow light emitting material S decreases, and there is a problem that measurement accuracy of the luminescence quantum yield cannot be sufficiently obtained.
In contrast, in the measurement method using the spectroscopic measurement apparatus 1 according to the present embodiment, first, in the spectral data acquisition step, switching control of on/off of the light source 2 by the control unit 22 and control of the exposure time of the detection light by the spectroscopic detector 4 are performed. Fig. 4 is a diagram showing an example of control of the time profile of the intensity of light emission and the exposure time of detection light in the long afterglow light emitting material. In the spectral data acquisition step, as shown in fig. 4, the 1 st period T is started together with the start of the output of the excitation light by the light source 21And acquisition of spectral data of the detected light in the spectral detector 4 is started. During the 1 st period T1In this case, the long afterglow light emitting material S is continuously irradiated with excitation light while the excitation light is kept being input into the internal space 11. Thereby, the long afterglow luminescent material S is excited to start luminescence. During the 1 st period T1The long afterglow phosphor S has a constant peak intensity after increasing the luminescence. The exposure time for the detection light in the spectroscopic detector 4 is set to the exposure time t that is the shortest for the entire measurement period so that saturation of the signal in the spectroscopic detector 4 does not occur1. In the example of FIG. 6, the exposure time t1For example 20 msec.
During the 1 st period1Then 2 nd period T2In (2), the output of the excitation light by the light source 2 is stopped. During period 2T2In the above description, the incidence of the excitation light to the long-afterglow light-emitting material S is stopped, but the light emission of the long-afterglow light-emitting material S in which the excitation light is accumulated is continued for a certain period of time while gradually attenuating. Period 2T2The timing of the start of (b) is determined based on, for example, the peak of the intensity of light emission. In this case, the 1 st period T is monitored by the spectroscopic detector 41Luminescence inWhen the variation per unit time of the peak value of the intensity of light emission is equal to or less than the threshold value (for example, 1%), the output of the excitation light from the light source 2 is stopped.
In addition, during the 2 nd period T2In the spectral detector 4, the exposure time of the detection light is set to be longer than the 1 st period T1Exposure time t in (1)1Exposure time t2. Exposure time t2The exposure time t can also be adjusted1Multiplied by an arbitrary constant. In addition, the exposure time t2The ratio of the intensity peak of the excitation light to the intensity peak of the emitted light may also be used for determination. In this case, the 1 st period T is monitored by the spectroscopic detector 41The ratio of the intensity peak value of the excitation light and the intensity peak value of the emitted light in (2) (peak acquisition step) is calculated by dividing the intensity peak value of the excitation light by the intensity peak value of the emitted light. Then, the calculated ratio is compared with the exposure time t1Multiplying to determine the exposure time t2. For example at exposure time t120msec and a ratio of 10, an exposure time t2Set to 200 msec. In calculating the ratio, it is preferable to use a value obtained by stabilizing the intensity as the peak value of the intensity of light emission.
Period 2T2Exposure time t of detection light in (1)2Can be maintained until the end of the measurement, but can also be from period 2T2The spectroscopic detector 4 is controlled in such a manner that the exposure time of the detection light becomes longer after a certain time has elapsed from the start. In this case, for example, a threshold value of the intensity of light emission is set in advance, and the period T is set in the 2 nd period2In (2), when the intensity of the emitted light is attenuated to be equal to or less than the threshold value, the exposure time for the detection light is set to be longer than the exposure time t2Exposure time t3. Exposure time t3The value of (A) is not particularly limited, and the exposure time t may be set, for example2Multiplying by an arbitrary coefficient to determine the exposure time t3. For example at exposure time t2200msec and a factor of 10, an exposure time t2Set to 2000 msec.
In the luminescence quantum yield analysis step, a time curve of the luminescence intensity of the long-afterglow luminescent material S is plottedDuring analysis, based on the 1 st period T1Exposure time t of the detecting light11 st period T1The intensity of luminescence of the long afterglow luminescent material S in (1) is normalized. Based on the 2 nd period T2Exposure time t of the detecting light22 nd period T2The intensity of luminescence of the long afterglow luminescent material S in (1) is normalized. During period 2T2After a certain time, the exposure period is self-exposed for time t2Set as an exposure time t3In the case of (1), the period after the set time is based on the exposure time t3Normalization is performed.
In the luminescence quantum yield analysis step, when the luminescence quantum yield of the long-afterglow luminescent material S is calculated based on the time curve of the luminescence intensity of the long-afterglow luminescent material S, the 1 st period T may be used1The number of absorption photons of the long afterglow luminescent material S is determined from the excitation light spectrum data of (1). In this case, specifically, for the calculation of the number of absorbed photons, first, an extraction window (a-B in fig. 3) is set for the spectrum S1 at the time of reference measurement and the spectrum S2 at the time of sample measurement, which are represented by the wavelength axis, and as shown in fig. 5, the excitation light spectrum data L1 at the time of reference measurement and the excitation light spectrum data L2 at the time of sample measurement are acquired with respect to the time axis, respectively. Secondly, from period 1T1The integrated value of the number of photons of the excitation light spectrum data L1 in (1) minus the period T1The integral value of the photon count in the excitation light spectrum data L2 is used to determine the absorption photon count of the long afterglow luminescent material S.
In addition, in the luminescence quantum yield analysis step, when the luminescence quantum yield of the long afterglow luminescent material S is calculated based on the time curve of the luminescence intensity of the long afterglow luminescent material S, it may be based on 1) the 1 st period T12) 2 nd period T2And 3) 1 st period T1And the 2 nd period T2Total period T of1+2The number of emission photons of the long afterglow luminescent material S is determined from the emission spectrum data in any period. In this case, for the calculation of the number of emitted photons, specifically, first, an extraction window is set for the spectrum S2 at the time of sample measurement represented by the wavelength axis (C-D in fig. 3). Then, the number of emitted photons passes through itself as shown in FIG. 6Emission spectrum data L3 obtained by subtracting the number of excitation light photons (reference measurement result) from the emission photons (sample measurement result) in the extraction windows C-D was obtained. Finally, the luminescence quantum yield of the long afterglow luminescent material S was calculated by dividing the number of luminescence photons by the number of absorbed photons.
As described above, in the spectrometry device 1, the 1 st period T during which the acquisition of the spectrum data is started1Excitation light is continuously input to the long afterglow luminescent material S in the integrator 3. The intensity of the excitation light is significantly higher than that of the luminescence of the long-afterglow luminescent material S. Therefore, compared with the 2 nd period T2Exposure time t of detection light in (1)2Make the 1 st period T1Exposure time t of detection light in (1)1The time becomes short, and thereby saturation of the signal in the spectral detector 4 can be prevented. In the spectroscopic measurement apparatus 1, the 1 st period T is continued1Then 2 nd period T2The input of excitation light to the long afterglow luminescent material S in the integrator 3 is stopped and the 2 nd period T is set2Exposure time t of detection light in (1)2Longer than the 1 st period T1Exposure time t of detection light in (1)1. Thus, light emission from the long-afterglow light-emitting material S, which has a significantly low intensity with respect to the excitation light and whose intensity fluctuates with time after the input of the excitation light is stopped, can be detected at a sufficient S/N ratio. Therefore, the spectroscopic measuring apparatus 1 can measure the luminescence quantum yield of the long afterglow luminescent material S with high accuracy. In addition, by making the exposure time t2Is longer than the exposure time t1Even when the long-afterglow luminescent material has a long luminescence lifetime, the increase in the amount of data necessary for acquiring spectral data can be suppressed.
In the spectroscopic measurement apparatus 1, the control unit 22 may be configured to perform the second period T from the 2 nd period T2The spectroscopic detector 4 is controlled in such a manner that the exposure time of the detection light becomes longer after a certain time has elapsed from the start. This makes it possible to more favorably suppress an increase in the data amount required for acquiring the spectral data.
In the spectroscopic measurement apparatus 1, the spectroscopic detector 4 acquires the 1 st period T based on the spectral data1Peak intensity of internal excitation light and long afterglow luminescenceThe control section 22 controls the intensity peak of the emitted light of the material S based on the ratio of the intensity peak of the excitation light to the intensity peak of the emitted light and the 1 st period T1Exposure time t of the detecting light1Determines the 2 nd period T by the product of2Exposure time t of the detection light at the start of (1)2. By using such a ratio, the 2 nd period T can be set2Exposure time t of the detection light at the start of (1)2Optimization can prevent saturation of the signal in the photodetector 4 in the 2 nd period T2.
In the spectroscopic measurement apparatus 1, the analysis unit 21 passes the time period T based on the 1 st period1Exposure time t of the detecting light1While the 1 st period T1Based on the 2 nd period T2Exposure time t of the detecting light2While the 2 nd period T2The long-afterglow luminescent material S in (1) is normalized in the emission intensity, and the time curve of the emission intensity of the long-afterglow luminescent material S is analyzed. Thus, even when the exposure time is dynamically changed during the measurement period, the time curve of the emission intensity of the long-afterglow luminescent material S can be accurately analyzed.
In the above embodiment, the integrator 3 formed of an integrating sphere is used as shown in fig. 1, but an integrator 30 formed of an integrating hemisphere may be used as shown in fig. 7. The body 32 and the internal space 31 of the integrator 30 are formed in a hemispherical shape. The spherical portion of the inner wall of the body 12 is a wall surface having high reflectance and excellent diffusibility, and the flat surface portion is a flat mirror having high reflectance. The input unit 33 and the output unit 34 may be provided at any position of the spherical portion and the planar portion. Even in the case where the integrating hemisphere is used as the integrator 30 as described above, the luminescence quantum yield of the long afterglow luminescent material S can be measured with high accuracy.
Description of the symbols
1 … spectrometer, 2 … light source, 3, 30 … integrator, 4 … photodetector, 11 … internal space, 21 … analysis unit, 22 … control unit, S … long afterglow luminescent material, T …1… period 1, T2… at the 2 nd stage,t1… Exposure time, t, during period 12… exposure time during period 2.
Claims (10)
1. A spectroscopic measurement apparatus, wherein,
a spectroscopic measuring apparatus for measuring the quantum yield of luminescence by irradiating a long afterglow luminescent material with excitation light,
the disclosed device is provided with:
a light source that outputs the excitation light;
an integrator having an internal space in which the long-afterglow luminescent material is disposed, the integrator outputting light from the internal space as detection light;
a spectroscopic detector that disperses the detection light to obtain spectral data;
an analysis unit that analyzes the emission quantum yield of the long-afterglow luminescent material based on the spectral data; and
a control unit that controls switching of the presence or absence of input of the excitation light into the internal space and an exposure time of the detection light in the spectral detector,
the control unit controls the light source to maintain the input of the excitation light into the internal space during a 1 st period in which the spectroscopic detector starts acquiring the spectral data and to stop the input of the excitation light into the internal space during a 2 nd period subsequent to the 1 st period, and controls the spectroscopic detector to make the exposure time of the detection light in the 2 nd period longer than the exposure time of the detection light in the 1 st period.
2. The spectroscopic measurement apparatus according to claim 1, wherein,
the control unit controls the spectral detector such that the exposure time of the detection light becomes longer after a predetermined time has elapsed from the start of the 2 nd period.
3. The spectroscopic measurement apparatus according to claim 1 or 2, wherein,
the spectral detector obtains an intensity peak of the excitation light and an intensity peak of the emission light of the long-afterglow luminescent material in the 1 st period based on the spectral data,
the control unit determines the exposure time of the detection light at the start of the 2 nd period based on a product of a ratio of an intensity peak of the excitation light to an intensity peak of the emission light and the exposure time of the detection light in the 1 st period.
4. The spectroscopic measurement apparatus according to claim 1 to 3, wherein,
the analysis unit analyzes a time curve of the emission intensity of the long-afterglow luminescent material by normalizing the intensity of the emission of the long-afterglow luminescent material in the 1 st period based on the exposure time of the detection light in the 1 st period and normalizing the intensity of the emission of the long-afterglow luminescent material in the 2 nd period based on the exposure time of the detection light in the 2 nd period.
5. The spectroscopic measurement apparatus according to claim 1 to 4,
the integrator is an integrating hemisphere.
6. A spectroscopic measurement method in which, in a spectroscopic measurement,
is a spectroscopic measurement method for measuring the quantum yield of luminescence by irradiating a long afterglow luminescent material with excitation light,
the disclosed device is provided with:
a spectral data acquisition step of obtaining spectral data by splitting detection light output from an integrator having an internal space in which the long-afterglow light-emitting material is disposed, by a spectral detector; and
a luminescence quantum yield analysis step of analyzing the luminescence quantum yield of the long-afterglow luminescent material based on the spectral data,
in the spectral data acquisition step,
maintaining the input of the excitation light to the internal space during a 1 st period in which the acquisition of the spectral data is started by the spectroscopic detector, and stopping the input of the excitation light to the internal space during a 2 nd period subsequent to the 1 st period,
the exposure time of the detection light in the 2 nd period in the spectroscopic detector is made longer than the exposure time of the detection light in the 1 st period.
7. The spectroscopic measurement method according to claim 6, wherein,
in the spectral data acquisition step, the exposure time of the detection light in the spectral detector is made longer after a predetermined time has elapsed from the start of the 2 nd period.
8. The spectroscopic measurement method according to claim 6 or 7, wherein,
further provided with: a peak acquisition step of acquiring an intensity peak of the excitation light and an intensity peak of light emission of the long-afterglow light-emitting material in the 1 st period based on the spectral data,
in the spectral data acquisition step, the exposure time of the detection light at the start of the 2 nd period is determined based on the product of the ratio of the intensity peak of the excitation light to the intensity peak of the emission light and the exposure time of the detection light in the 1 st period.
9. The spectroscopic measurement method according to claim 6 to 8, wherein,
in the luminescence quantum yield analysis step, a time curve of the luminescence intensity of the long-afterglow luminescent material is analyzed by normalizing the intensity of the luminescence of the long-afterglow luminescent material in the 1 st period based on the exposure time of the detection light in the 1 st period and normalizing the intensity of the luminescence of the long-afterglow luminescent material in the 2 nd period based on the exposure time of the detection light in the 2 nd period.
10. The spectroscopic measurement method according to claim 6 to 9, wherein,
an integrating hemisphere is used as the integrator.
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